(1) Field of the Invention
The present invention relates to novel polyamide compositions and to a process for synthesizing these compositions. The polymerization reaction is between a cyclic xcex1,xcex2-unsaturated lactone and a R-substituted amide moiety substituted alkylene amine of the formula: 
R preferably has aligned diacetylene groups which provide a conductive polymer. Preferably, the polymer compositions are synthesized from 2 (5H)-furanone and the amine.
(2) Description of the Related Art
In the past, the desirable physical properties of organic polymers were relatively simple to evaluate. Of interest were ordinary attributes such as transparency, flexibility, heat and electrical conductance, water resistance, and pliability. These physical requirements could be met by any one of a wide variety of polymeric materials fabricated by one of several polymerizing reactions. These reactions include the polymerization of alkenes (e.g. polypropylene and polyvinylchloride), the condensation of acids and bases to form polyesters, or acids and amines to form polyamides.
More recently, there has been much effort to fabricate organic polymeric materials with more sophisticated properties. These include materials that can conduct electricity, that are magnetic, and materials that change some property, such as color or refractive index, under the influence of various external factors such as pressure, electric fields, magnetic fields, pH changes, or temperature alterations. In all of these applications, one critical requirement is that some functional group or groups along the polymer backbone be aligned in a regular repeating fashion with a very high density. Polymeric materials with very different properties can be made depending on the choice of the functional groups. Electron donor-acceptor pairs can be conductive or have optical properties that are influenced by electric or magnetic fields. Such polymeric materials have applications in sensor devices and optical switches. An array of negatively charged groups is a typical arrangement sought for conducting organic polymers where the charge carriers are metal ions and protons. Hydrogels can be formed if charges are present on the side chains. Materials with special conductive, magnetic or electro-optical properties can be fabricated from polymers having specialized aromatic side chains.
There are several methods for introducing side chains into a main chain polymer. One strategy is to add the side chains to the preformed main chain. This is generally not satisfactory because of the lack of predictability and reproducibility of stoichiometry, under-derivitization for stearic reasons, difficulty in accessing the interior of the polymer, poor solubility of the polymer, and inefficient coupling reactions. Alternatively, the desired side chain can be attached to each polymer monomer prior to chain formation. This method is generally more efficient but the subsequent coupling of the monomers often requires activating groups to be attached to one or both coupling sites. For example, the preparation of polyesters and polyamides require that the carboxylic acid function be activated before chain formation. Afterwards, the spent activating group has to be removed from the product. Radical polymerization cannot be used for side chains that contain unsaturations or heteroatoms such as sulfur which act as quenching agents for radicals. Furthermore, side chains containing reactive groups such as carboxylic acids often have to be protected before coupling. Finally, synthesis of most polymers is dependent on fossil fuels, which is a non-renewable resource that is rapidly being depleted, and is a major import product which affects the balance of trade.
Examples of polymers that are polyamides which can be synthesized from renewable resources are set forth below. U.S. Pat. No. 2,274,831 to Hill discloses polyamides and the preparation of polyamides by polymerizing amino acids containing as a heteroatom a tertiary amino nitrogen or by reacting diamines and dibasic acids, either or both of which contain a heteroatom of tertiary amino nitrogen. U.S. Pat. No. 2,691,643 to Chirtel et al discloses preparation of polypeptides of beta-alanine and amide forming derivatives of beta-alanine, beta-alanine alkyl esters, beta-alanine amides by self-condensation to produce water insoluble polypeptides which are useful for forming synthetic edible films. U.S. Pat. No. 2,786,045 to Chirtel et al discloses polymers of hydroxyacyl-amino acids and their polymers for the preparation of tough, elastic fibers and films. U.S. Pat. No. 2,968,629 to Thompson discloses a method of inhibiting metal corrosion using a condensation product of beta-lactone. U.S. Pat. No. 3,525,718 to Derieg et al discloses a process for producing a polyamide resin from beta-lactone. The process consists of reacting beta-lactone under anhydrous conditions at reduced temperatures to produce an amino acid addition product, and then in a subsequent step subjecting said product to polymerization conditions at elevated temperatures in which said product is substantially dehydrated to form a polyamide resin which is linear without side chains. The resin has properties that suggest it may be used in applications where nylon and Dacron have been used. All of the above mentioned inventions disclose process to make a specific product.
The proper alignment of the acetylene groups in long chain diacetylenes is one of the most difficult aspects of the fabrication of such materials. The acetylene functions need to be within a very defined distance of each other or separate chains with a tolerance of only 0.5 Angstroms. There are also quite strict requirements for the relative angles between diacetylene groups participating in the polymerization process (Villenave, E., et al., J. Phys. Chem. B 1997, 101, 8513-8519; Umemura, J., Kamata, T., Kuwai, T., Takenaka, T., J. Phys. Chem., 1990, 94, 62-67; Batchelder, D. N., Evans, S. D., Freeman, T. L., Haussling, L., Ringsdorf, H., Wolf, H., J. Am. Chem. Soc. 1994, 116, 1050-1053; Lando, J. B. in Polydiacetylens; Bloor, D., Chance, R., Eds.: Nijhoff: Dordrechet, The Netherlands, 1985) in each chain. Several strategies have been tried in attempts to accomplish this, the most common one being to align the chains on a flat support such as a highly polished gold surface to form self assembled monolayers (Mowery, M. D., Menzel, H., Cai, M., Evans, C. E., Langmuir, 1998, 14, 5594-5602; Kim, T., Chan, K. C., Crooks, R. M., J. Am. Chem. Soc. 1997, 119, 189-193; Shirai, E., Urai, Y., Itoh, K. J. Phys Chem. B 1998, 102, 3765-3772; Kim, T., Crooks, R. M., Tsen, M., Sun, L., J. Am. Chem. Soc. 1995, 116, 3963-3967). The molecules are generally anchored to the surface via thiol groups. This method works well for saturated alkane thiols but there are some problems with alkyl chain containing diacetylene groups. Because of the large atomic radius of gold compared to carbon, variations in the surface of only a few gold atoms put the acetylene functions in the aligned chains out of register, thus terminating polymerization. It is therefore very difficult to obtain any high degree of conjugation. The substrate surface pretreatment also plays an important role in the degree of polymerization. This method is also extremely labor-intensive. Another shortcoming of the method is the tendency for the thiol to form disulfide bonds. When this happens, the chains are not aligned and polymerization is inhibited, with decreasing local and long range order (Mowery, M. D., Evans, C. E., J. Phys. Chem. B 1997, 101, 8513-8519; Mowery, M. D., Menzel, H., Cai, M., Evans, C. E., Langmuir, 1998, 14, 5594-5602). Thiols are also very prone to oxidation by air to give oxy-species that degrade the integrity of the films. Another drawback of films that are formed on metal supports is that they cannot be used for applications that require transmission of light.
Langmuir Blodgett technology presents another approach to generating monolayers of hydrocarbons containing polydiacetylene groups (Saito, A., Urai, Y., Itoh, K., Langmuir 1996 12, 3938-3944; Charych, D. H., Nagy, J. O., Spevak, W., Bednarski, M. D., Science 1993, 261, 585-588; Berman, A., Ahn, D. J., Lio, A., Salmeron, M., Reichert, A., Charych, D., Science 1995, 269, 515-518; Mino, N., Tamura, H., Ogawa, K., Langmuir 1992, 8, 594-598). This is an excellent method for preparing limited number of highly ordered films for experimental analyses and studies. It suffers from the drawback of being a very labor-intensive method. Langmuir Blodgett films are also not stabilized by covalent forces between the molecular units and therefore unstable to a variety of chemical or physical conditions. It is certainly not applicable for large scale commercial applications where films have to be packaged and must withstand shock and handling.
Polydiacetylenes have much potential as new organic materials in electrical conductivity, non-linear optical and near-infrared active applications (Green, B. I., Orenstein, J., Schmitt-Rink, S., Science 1990, 247, 679-687; Kim, W. H., Bihari, B., Moody, R., Kodali, N. B., Kumar, J., Tripathy, S. K., Macromolecules 1995, 28, 642-647; Sukwattanasinitt, M., Wang, X., Li, L., Jiang, X., Kumar, J., Tripathy, S. K., Sandman, D. J., Chem. Mater 1998, 10, 27-29; Huggins, K. E., Son, S., Stupp, S. I., Macromolecules 1997, 30, 5305-5311; Molyneux, S., Kar, A. K., Wherrett, B. S., Axon, T. L., Bloor, D., Optics Letters, 1993, 18, 2093-2095; Sandstedt, C. A., Eckhardt, C. J., Downey, M. J., Sandman, D. J., Chem. Mater. 1994, 6, 1346-1350). U.S. Pat. No. 6,194,529 to Hollingsworth and Wang describes polyacetylene compounds with improved properties which are not in the form of polymers. The fabrication of 2-dimensional systems in which the polyacetylene function occurs as a band sandwiched between two aliphatic layers are especially of interest (Okada, S., Peng, S., Spevak, W., Charych, D. Acc. Chem. Res. 1998, 31, 229-239; Kuo, T., O""Brien, D. F. J. Am. Chem. Soc. 1988, 110, 7571-7572; Charych, D. et al Chem Biol. 1996, 3, 113-120; Mullen, K., Rabe, J. P. Mol. Elec. Sci. Tech. 1998, 852, 205-218; Dorn, I. T., Hofmann, U. G., Peltonen, J., Tempe, R., Langmuir, 1998, 14, 4836-4842).
The polymerization process used in the present invention is generally described in U.S. Pat. No. 6,153,724 granted Nov. 28, 2000. This process provides the starting point for the present invention.
This invention is related to a process for the preparation of a polyamide polymer which comprises:
(a) reacting in a single step in a reaction mixture an xcex1,xcex2-unsaturated lactone and an amine of the formula: 
xe2x80x83wherein alkylene contains 1 to 50 carbon atoms and wherein amine in the formula is a moiety selected from the group consisting of xe2x80x94NH2 and xe2x80x94NH3+ and mixtures thereof and wherein each of the R can be the same or different and contain 1 to 50 carbon atoms; and
(b) separating the polyamide polymer from the reaction mixture, wherein multiple 
xe2x80x83groups are in vertically aligned spaced relationship along a polyamide backbone.
The present invention particularly relates to a process for the preparation of a polyamide polymer which comprises:
(a) reacting in a single step in a reaction mixture xcex1,xcex2-unsaturated lactone and an amine of the formula 
xe2x80x83wherein amine in the formula is a moiety selected from the group consisting of xe2x80x94NH2 and xe2x80x94NH3+ and mixtures thereof, wherein each of the R can be the same or different and contain 1 to 50 carbon atoms to produce a polyamide polymer in the reaction mixture of the formula; 
xe2x80x83wherein n is between about 1 and 50; and
(b) separating the polyamide polymer from the reaction mixture, wherein multiple of Rxe2x80x94 have at least some adjacent carbon atoms with unsaturation which are aligned adjacent to each other.
This invention is further related to a polyamide prepared by reacting xcex1,xcex2-unsaturated lactone with an Rxe2x80x94 substituted amide moiety substituted alkylene amine of the formula 
wherein alkylene contains 1 to 50 carbon atoms and wherein amine in the formula selected from the group consisting of xe2x80x94NH2 and xe2x80x94NH3+ and mixtures thereof, wherein multiple of the R are in vertically aligned and spaced relationship along a polyamine backbone, wherein each of the R can be the same or different and contain 1 to 50 carbon atoms and optionally are positively or negatively charged.
Also, this invention is related to a polyamide of the formula: 
wherein n is between about 1 and 50, wherein R contains between 1 and 50 carbon atoms and is optionally substituted with heteroatoms O, N, S, and P and combinations thereof which allow the formation of a polyamide polymer wherein each of the R can be the same or different and contain 1 to 50 carbon atoms, and wherein R can be positively or negatively charged.
It is an object of the present invention to provide polyamide polymers with side chains, preferably having carbon to carbon unsaturation, derived from xcex1,xcex2-unsaturated lactones and an R amide moiety substituted alkylene amine of the formula 
Another object of the present invention is to provide polyamide polymer compositions and a process for preparing them wherein R is formed with aligned diacetylene groups suitably positioned for polymerization.
A further object of the present invention is to provide polymer compositions which are economical to prepare.